Control of bacteria with detergent or cleaning compositions containing phenylthioureas

ABSTRACT

Beta -Chlorallylthioureas as well as their derivatives obtained by adding Cl2 or Br2 at the chlorallyl group are effective microbicides. They may be used as active agents in detergents or for the purpose of imparting to fibrous materials anti-microbial and anti-mycotic resistance as well as for controlling plantpathogenic bacteria and fungi.

United States Patent Hubele i *July 8, 1975 1 CONTROL OF BACTERIA WITH[56] References Cited DETERGENT OR CLEANING UNITED STATES PATENTSCOMPOSITIONS CONTAINING 2,846,399 8/1958 Beaver a a1 252/107PHENYLTHIOUREAS 2,894,986 7/1959 Beaver et al 260/553 3,200,035 8/1965Martin et al. 252/106 X ['75] Inventor' Hubele Rlehen swtzerland3,395,233 7/1968 Duerr et a1. 424/322 Assignee: AG, Basel SwitzerlandMartin et al v 3,686,418 8/1972 Taber et al. 424/322 1 1 Nome: The Pomon9f the term of thls 3,811,932 5/1974 Hubele 252/8.8 x

patent subsequent to May 21, 1991, has been disclaimed.

22 Filed; May 8, 1972 Primary Examiner--P. E. Willis, .11.

Attorney, Agent, or F irmFreder1ck H. Rabin [21] App]. No.: 250,937

' Related [1.8. Application Data [62] Division of Ser. No. 34,594, May4, 1970, TRACT abandoned' B-Chlorallylthioureas as well as theirderivatives 0btained by adding Cl or Br at the chlorallyl group are [30]Apphcanon Pnomy Data effective microbicides. They may be used as activeMay 7, 1969 Switzerland 7008/69 aggms in detergents or for the purposeof imparting to July 25, 1969 Switzerland 1 1440/69 fibrous materialsanti-microbial and anti-mycotic resistance as well as for controllingplant-pathogenic bac- [52] US. Cl. 252/106; 252/107; 117/138.5 t i a dfungi. [51] Int. Cl Clld 3/48 [58] Field of Search 252/106, 107;424/322;

3 117/ 1 38.5 15 Claims, N0 Drawings CONTROL OF BACTERIA WITH DETERGENTOR CLEANING COMPOSITIONS CONTAINING PHENYLTI-IIOUREAS This is a divisionof application Ser. No. 34,594, filed on May 4, 1970, now abandoned.

This invention provides new biocidal thioureas of the formula which alsoincludes derivatives thereof obtained by the addition of C1 or Br at thechlorallyl group, and in which Ar represents a phenyl group which may beunsubstituted or substituted by one or more of the following residues;halogen, N --CN, SCN, alkyl or haloalkyl with up to 4 carbon atoms thelatter group preferably being CF CF CI, -CFCl or CCI As halogens thereare to be understood fluorine, chlorine, bromine or iodine, preferablychlorine and bromine.

Those compounds are preferred in which the phenyl group is substitutedby not more than three of the said substituents. Especially activecompounds of the formula I are those containing substituents in the 3,4or 3,5-positions of the phenyl nucleus. The substituents are preferablyelectronegative electron drawing), but this does not exclude thesimiltaneous presence of electroneutral substituents such as methyl,ethyl, npropyl. isopropyl, n-butyl or sec.-butyl groups.

The active substances of the formula I are active against humanandplant-pathogenic bacteria and fungi.

They have a very good activity against members of the classphycomycetes, for example, phytopathogenic fungi such as Botrytis andPiricularia, but also against various other pathogens on corn, soyabeans, maize, rice, vegetables fruit and other cultivated plants.

They are particularly active against the following species of fungi:species of Cochliobolus miyabeanus, species of Corlicium, species ofCeruspora, species of Alternaria,

Venturia inaequalis, Podosphaera leucotricha, Uromyces p/zaseoli, Cercospora apii, Cercospora beticola, Cercospora musae, Piricularia sp.,Erysiphe cichoriacearum, Penicillium digitatum, Sphaerot/reca llumuli,Diplocarpon rosae, Uncinula necalor, Coccomyces hiemalis, Cladosporiumcarpophilum, Erysiphe graminis lwrdei, Munulinia (Sc lerotinia) Laxa,Monolinia (Sclerotinia) fructicola, Piricularz'a oryzae, Pucciniarecondita, Puccinia coronata, Pucc'inia glumarum, Puccinia graministritici, Aspergillus niger, Aspergillus terreus, Rhizoctonia, Fusarium,Verticillium. This list is not intended to be complete.

The active substances of the invention and preparations containing themalso exhibit a toxic action on fungi that attack plants in the earth andsome of which cause tracheomycoses, such as Fusarium cubense, Fusariumdianthi, Verticillium alboatrum and Phialophora cinerescens.

The active substances of this formula I can also serve asbacteriostatics, for example, as additions to soap, that is to say, theycan be used principally in detergent and cleaning preparations.

For this purpose there have been found especially suitable the compoundsof the formula R NH-C-N-CH in which two of the substituents R, R and R"are identical or different from each other and represent C1 or CF andthe third represents a hydrogen atom.

The present invention also provides biocidal preparations, which containas active components at least one thiourea of the formula I, or aderivative thereof produced by the addition of C1 or Br to the clorallylgroup, together with one or more of the following additives: solvents,dispersing agents, wetting, agents, adhesives, binding or thickeners ordiluents, stabilisers or further The active components can also be usedin the textile field. When applied from aqueous dispersions or fromsolutions in organic solvents they possess an affinity for keratinfibres and can be used for protecting these fibres against attack bymicro-organisms.

In the presence of protein materials, for example, blood or serum, andnon-ionic, anionic or cationic organic surface-active compounds, such asare present in the form of soaps and synthetic wetting, emulsifying orwashing agents, they do not lose their biocidal action. Moreover theyhave no objectionable odour, they are well tolerated by healthy skin andthey cause no poisonous side effects towards warrn blooded animals inthe concentrations customarily used in disinfection.

All these properties render the detergent and cleaning preparations ofthis invention suitable for a very wide range of application. Thus, forexample, there may be mentioned their use in the soap industry, incosmetics, and generally in the care of the body and hygiene asdisinfecting and preserving agents for a very wide variety of technicaland natural products, and especially as detergent and cleaningpreparations having a disinfecting and sanitizing action in houses andin industry. For these purposes they can be used in a very wide varietyof forms. As examples there may be mentioned their use in the form ofsoap solutions, foam baths, sprays, especially foam sprays, solutions inorganic solvents and the like. These applications are connected withbiocidal finishing which is mainly antibacterial and anti-mycotic.

Of special interest, however, is the use of the detergents and cleaningagents of the invention for imparting an anti-microbial and anti-mycoticfinish in or with the protection of textile and non-textile fibrousmaterials and laminar structures such as films, which may be in anystage of manufacture, against micro-organisms. The treatment of fibrousmaterials is especially important, because it has been found that theactive substances of the formula (I) when applied from an aqueous bathexhibit a substantive affinity for a very wide variety of fibrousmaterials.

As fibrous materials there come into consideration natural and syntheticfibres. Among natural fibres there may be mentioned, in addition tomineral fibres, for example, asbestos, more especially cellulosicfibres, such as linen, sisal, cocus, bast, and especially cotton andnitrogenous fibres, such as leather and wool. As synthetic fibrousmaterials there come into consideration both polycondensates such aspolyadducts and polymerisation products, that is to say, polymers in awide sense, and also glass fibres. The polymer fibres may be derivedfrom natural or synthetic polymers. Fibres of nat ural polymers are, forexample, regenerated cellulose and cellulose dito tri-acetate-Fibresderived from synthetic polymers are, for example, fibres of polyesters,polyamides, polyurethanes, polyacrylonitrile, polyvinyl chloride andpolyethylene. In this manner it is possible to impart to these fibrousmaterials by simple washing with a detergent or cleaning preparation ofthe invention a finish that is lastingly biocidal, preferablyantibacterial and anti-mycotic, and thus to protect these materialsagainst attack by micro-organisms and other pests. Fibrous materialshaving a finish of this kind are not only themselves protected againstattack by microorganisms and moulds. They also protect their immediatesurroundings and thus prevent, for example, the occurrence of unpleasantbody and perspiration odours caused by microorganisms, which isespecially advantageous with fully synthetic and cellulosic textilefibrous materials. The finish so produced has a good resistance tochlorine and perborate.

The detergent and cleaning preparations of the invention contain, inaddition to the active substance of the formula (I), solid or liquidadditions that are suitable for this purpose. Such additions are, forexample, the usual washing assistants and washing-active substances.Washing-active substances are surface-active compounds. Suchsurface-active compounds are, for example, soaps, that is to say, salts,especially alkali metal salts, of fattyacids of high molecular weight,or soap-free washing-active substances, for example, anion-activealkyl-aryl sulphonates, tetrapropyl-benzene sulphonates, fatty alcoholsulphonates, condensation products of fatty acids and methyl-taurine,condensation products of fatty acids with salts of oxyethane sulphonicacids, fatty acidprotein condensation products, primary alkylsulphonates, non-ionic products, for example, condensation products ofalkyl-phenols and ethylene oxides and also cation-active compounds. Aswashing assistants there are to be understood compounds which themselvespossess no or only a small washing power, but influence the washingproperties of a detergent. Thus, for example, they are able to impart anoptimum pI-I-value to the washing liquor or to increase thedirt-tolerance capacity and the washing effect. Examples of suchsubstances are electrolytes, for example, trisodium phosphate, sodiumdiphosphate, sodium carbonate, sodium bicarbonate, sodium sulphate,sodium metasilicate or water glass, cellulose glycolates, organiccomplex-formers (softeners), bleaching agents, optical brighteners,light protection agents, anti-oxidants, perfumes etc.

The new preparations of the invention may be in various forms dependingon their mode of use, for example, in the form of solid, semi-solid orliquid soaps, in the form of pastes, powders, emulsions, suspensions,solutions in organic solvents, or sprays, powders, granulates, tablets,in capsules of gelatine or other material, or as salves.

The quantities in which the active substances of the formula (I) areused may vary within a wide range. Generally, however, 1 to 30 grammesper litre of liquor produce the desired effect. The detergent andcleaning preparations generally have a content of active substance of0.3 to l0% by weight, and preferably 0.5 to 3% by weight.

As further ingredients the preparations of the invention may contain,depending on the purpose for which they are to be used, other biocidalsubstances, preferably fungicides or microbicides.

As components of the combination there may be mentioned, for example,the following active substances:

INORGANIC COMPOUNDS elementary sulphur ammonium polysulphide sodiumpolysulphide barium polysulphide calcium polysulphide and calciumthiosulphate (lime sulphur) calcium hypochlorite boric acid sodiumtetraborate decahydrate (borax) zinc chloride magnesium borate nickelsulphate potassium chromate lead arsenate cadmium chloride cadmiumcarbonate COPPER COMPOUNDS TIN AND MERCURY COMPOUNDSbis-(tri-n-butyl-tin) oxide triphenyl-tin hydroxide (fentin hydroxide)triphenyl-tin acetate (fentin acetate) bis-(tributyl-tin) succinatemercurous chloride (calomel) mercuric chloride mercuric oxide mercuryzinc chromate complex mercuric lactate ethyl-mercuri chloride2-hydroxyethyl-mercuri acetate ethyl-mercure isothiocyanate3-ethoxypropyl-mercuri bromide chloromethoxypropyl-mercuri acetatemethoxyethyl-mercuri chloride 2-methoxyethyl-mercuri silicatebis-(methyl-mercuri) sulphate bis-(methyl-mercuri) ammonium acetateethyl-mercuri acetate 2-methoxyethyl-mercuri acetate ethyl-mercuriphosphate isopropylmethyl-mercuri acetate methyl-mercuri cyanidemethyl-mercuri benzoate N-cyano-N-(methyl-mercuri)-guanidinemethyl-mercuri pentachlorophenolate ethyl-mercuri 2,3-dihydroxypropylmercaptide methyl-mercuri S-hydroxyquinolate (Ortho LM)N-(methyl-mercuri)-1,4,5,6,7,7-hexachloro-bicycl- [2.2.]hept-5-en-2,3-dicarboximideN-(ethyl-mercuri)-l,4,5,6,7,7-hexachloro-bicyclo- [2.2.1hept-5-en-2,3-dicarboximide sodium salt of ethyl-mercuri thiosalicylateN-(ethyl-mercuri)-p-toluene sulphonic acid anilide phenyl-mercuriacetate (PAM) phenyl-mercuri propionate phenyl-mercuritriethanolammonium lactate (PAS) phenyl-mercuri ureaN-(phenyl-mercuri)-l ,4,5,6,7,7-hexachloro-bicyclo- [2.2.1]hept-S-en-2,3-dicarboximide phenyl-mercuri dimethyl dithiocarbamatephenyl-mercuri formamide phenyl-mercuri chloride phenyl-mercuri acetatephenyl-mercuri benzoate phenyl-mercuri borate phenyl-mercuri hydroxidephenyl-mercuri iodide basic phenyl-mercuri nitrate phenyl-mercurimonoethanolamine lactate phenyl-mercuri salicylate hydroxy-mercurichlorophenol hydroxy-mercuri trichlorophenol hydroxy-mercuri nitrophenolN-phenyl-mercuri ethylene diamine phenyl-mercuri monoethanolammoniumacetate pyridyl-mercuri acetate diphenyl-mercuri 8-hydroxyquinolatemercuric complex with organic phosphates mixture of methyl-mercuri2,3-dihydroxypropyl mercaptide and methyl-mercuri acetate mixture ofethyl-mercuri 2,3-dihydroxypr0pyl mercaptide and ethyl-mercuri acetatemixture of hydroxy-mercuri chlorophenol and hydroxy-mercuri nitrophenolmercury cadmium organic complex FURTHER ORGANIC METAL COMPOUNDS.

cadmium succinate cadmium di-n-propyl-xanthate cadmium8-hydroxyquinolate phenylamino-cadmium acetate phenylamino-cadmiumdilactate methyl-arsine sulphide zinc octoate zinc oleate IIMPLE ORGANICCOMPOUNDS (ALIPHATICS).

formalin paraform aldehyde acrolein methyl bromide methyl isothiocyanatetetraiodo-ethylene 1,3-dichloropropylene and related chlorinated Chydrocarbons 1-chloro-3-bromopropyIene-( l trans-l ,4-dibr0mobutylene(2) l,3-dichloropropylene-( l l-chloro-2-nitropropane 2-ch1orol-nitropropane trichloro-nitromethane dichloro-tetrafluoro-acetone sodiumsalt of propionic acid calcium salt of propionic acid chlorofumaric acidbis-B-chlorethyl ester sorbic acid and its potassium salt 2-propylene-l,1-diol acetate 2-aminobutane dodecyl-guanidine acetate (dodine)dodecyl-guanidine phthalate a-chloracetyl-l ,3-aminopropionitrilea-bromacetyl-valine amide 1,2-dichlorol -(methylsulphonyl )-ethylene1,2-dichloro- 1 -(butylsulphonyl)-ethylenetrans-1,2-bis-(n-propylsulphonyl)-ethylene BENZENE DERIVATIVES.

p-dichlorobenzene hexachlorobenzene (HCB)l,2,4,5-tetrachloro-4-nitrobenzene (tecnazene) pentachloro-nitrobenzene(quintozene) 1 ,3,5-trichloro-2,4,6-trinitrobenzene isomeric mixture ofl ,3 ,4-trichloro-2,6- dinitrobenzene and l ,2,3-trichloro-4,6-dinitrobenzene 2,4,5,6-tetrachloro-isophthalic acid nitrile2,4-dinitrophenyl thiocy-anate diphenyl (biphenyl) o-nitro-diphenyl1-chloro-2,4-dinitronaphthalene acenaphthene PI-IENOLS.

sul-

salicyl-anilide bismuth salicylate trifluoromethyl-salicyl-anilidehalogenated with chlorine or bromine brominated salicyl-anilide(3,5-dimethyl-4-chlorophenoxy)-3thanol DINITROPI-IENOL DERIVATIVES.

ANILINE DERIVATIVES.

2,6-dichloro-4-nitraniline (dichloran) 2-cyanethyl-N-phenyl carbamatepropynyl-N-phenyl carbamate a-(2-bromacetoxy)-acetanilide QUINONEDERIVATIVES.

2,3,5,6-tetrachloro-benzoquinone-(1,4) (chloranil)2,3-dichloro-naphthoquinone-( 1,4) (dichlone)Z-amino-3-chloro-naphthoquinone-( 1,4)2-chloro-3-acetylamino-napthoquin0ne-( 1,4)4-methyl-2,3,5,l0-tetrahydro-3,5,lO-trioxo-4I-I4-H- naphth0-( 2,3 ,-b)-l,4-thiazine 2,3,6,7-tetrachloro-4a,8a-epoxy-l ,2,3,4,4a,8a-

hexahydro- 1 ,4-methanonaphthalene-5 ,8-dionequinone-oxime-benzoyl-hydrazone (benquinox)TRICHLOROMETI'IYLTI-IIO-DERIVATIVES.

N-(trichloromethylthio)-phthalimide (folpet) N-(trichloromethylthio)-cyclohex-4-en-l ,2

dicarboximide (captan) N-( I ,l,2,2-tetrachlorethylthio)-cyclohex-4-en-1,2-

dicarboximide (captafol)N-methane-sulphonyl-N-trichloromethylthio-pchloranilineN'-dichlorofluoromethylthio-NN-dimethyl-N'- phenyl sulphonamide(dichlofluanide) S-( 2pyridyl- I -0xide )-S -trichloromethyl disulphidehydrochloride ORGANIC PHOSPHATES.

0,0,0-trimethyl thiophosphate 0,0-diethyl-phthalimido-phosphonothioate5-amino-bis-(dimethylamido)-phosphinyl-3-phenyl- 1,2,4-triazole(triamiphos) 5-methylamino-bis-(dimethylamido)-ph0sphinyl-3- phenyl-l,2,4-triazole 0,0-diethyl-O-Zpyrazinyl-phosphorthioateO-ethyl-S,S-diphenyl-dithiolphosphateO-ethyl-S-benzyl-phenyldithiophosphate0,0-diethyl-S-benzyl-thiolphosphate DITHIOCARBAMATES.

zinc salt of dithiocarbazinic acid sodium N-methyl-dithiocarbamate(metham) sodium N-methoxyethyl-dithiocarbamate crotonate sodiumN,N-dimethyl-dithiocarbamate (DDC) ammoniumN,N-dirnethyl-dithiocarbamate zinc N,N-dimethyl-dithiocarbamate (ziram)iron N.N-dimethyl-dithiocarbamate (ferbam) copperN,N-dimethyl-dithiocarbamate disodium ethylenel ,2-bis-dithiocarbamate(nabam) zinc ethylene-1,Z-bis-dithiocarbarhate (zineb) iron ethylenel,Z-bis-dithiocarbainate manganous ethylene-1 ,Z-bis-dithiocarbamate(maneb) calcium ethylenel ,Z-bis-dithiocarbamate ammonium ethylene-l,Z-bis-dithiocarbamate zinc propylene-1,2-bis-dithiocarbamate (mezineb)(propineb) bis-( dimethylthiocarbamyl )-ethylenel ,2-bisdithiocarbamatecomplex consisting of maneb and zinc salt (mancozeb) tetraethyl-thiurammonosulphide bis-(N,N-dimethyl-dithiocarbamylmercapto)- methylarsinetetramethyl-thiuram disulphide (thiram) dipyrrolidyl-thiuram disulphideN,N-bis-(dimethylamino)-thiuram disulphide polyethylene-thiuram sulphidecomplex consisting of zineb and polyethylenethiuram disulphide (metiram)O-l-IETEROCYCLES bis-(3,4-dichloro-2(5)-furanoyl)-ether (mucochloricanhydride) Z-methoxymethyl-S-nitrofurane S-nitro-furfuraldoxime-(Z)5-nitro-furfuryl-amidoxime-(2) l-oxy-3-acetyl-6-methyl-cyclohexene-( 5)-dione- (2,4) (dehydroacetic acid) l-N-HETEROCYCLES 3-[2-(3,S-dimethyl-Z-oxycyclohexyl)-2-hydroxyethyl]-glutarimide(cycloheximide) phthalimide 2- AND 3-N-l-IETEROCYCLES2-n-heptadecylimidazolidine acetate (glyodine)l-hydroxyethyl-2-heptadecyl-imidazolidine 1 -phenyl-3 ,5-dimethy1.-4-nitrosopyrazole 1-p-chlorphenyl-3,5-dimethyl-4-nitrosopyrazole I-p-sulphamylphenyl-3,5-dimethyl-4-nitrosopyrazolel-hydroxypyridine-2- N-( l-phenyl-Z-nitropropyl)-piperazine2-dimethylamino-6-methyl-5-n-butyl-4-hydroxypyrimidine N-dodeyl-l ,4,5,6-tetrahydropyrimidine N-dodecyl-2-methyl-1,4,5 ,6-tetrahydropyrimidine2-n-heptadecyl-tetrahydropyrimidine l-( 4-amino-4-propyl-5-pyrimidyl-methyl )-2-methylpyridinium chloride hydrochloride2-(2'-furyl)-benzimidazole (furidazole) 3-dodecyll-methyl-2-phenyl-benzimidazolium ferricyanide methyl N-benzimidazol-2-ylcarbamate (benomyl) 2-(o-chloranilino)-4,6-dichl0ro-sym.-triazine2-ethylamino-6-methyl-5-n-butyl-4- hydroxypyrimidine S-I-IETEROCYCLES5-chloro-4-phenyl-l ,2-dithiol-3-one 2,3-dicyano-l,4-dithia-anthraquinone (dithianone) 2-( 4-thiazolyl )-benzimidazoleNO-. NS- AND OS-HETEROCYCLES 4( 2-chlorophenyl-hydrazon0 )-3-methyl-5-isoxazolone (drazoxolone) thiazolidinone-4-thione-(2) (Rhodanine) 3-(p-chlorophenyl )-5-methyl-rhodanin 3 ,S-dimethyltetrahydrol,3,5-thiadiazine-2-thione (dazomet)3,3-ethylene-bis-(tetrahydro-4,6-dimethyl)-2I-I-l,3,5-thiadazine-2-thione (milneb)3-benzylidene-amino-4-phenyl-thiazoline'2-thione zinc salt of6-chlorobenzthiazole 2-thiol(a-B-diethylamino-ethoxy-Z-dimethylaminobenzthiazole dihydrochloridemonoethanolammonium-benzthiazle-2-thiollauryl-pyridinium--chloro-2-mercaptobenzthiazole zinc and sodium saltsof Z-mercaptobenzthiazole and dimethyldithiocarbamate6-(B-diethylaminoethoxy)-2- dimethylaminobenzthiazole dihydrochloride3-trichloromethylthio-benzothiazolone3-trichloromethylthio-benzoxazolone3-(trichloromethyl)-5-ethoxy-1,2,4-thiadiazole 6-methyl-2-oxo-l,3-dithiolo [4,5-b]-quinoxaline (quinomethionate) 2-thio-l,3-dithiolo[4,5-b1-quinoxaline (thioquinox) 2.3-dihydro5 -carboxanilido-6-methyl-l,4-oxathine 3 ,3 ,4,4-tetrachlorotetrahydrothiophene-l ,l-dioxide2,3-dihydro-5-carboxanilido-6-methyll ,4-oxathine- 4,4-dioxideQUATERNARY AM MONIUM COMPOUNDS cetyl-trimethylammonium bromiden-alkyl(C, ,C ,C ;)-dimethylbenzyl-ammonium chloridealkenyl-dimethylethylammonium bromide dialkyldimethylammonium bromidealkyldimethylbenzylammonium chloride alkyl C C,tolylmethyltrimethylammonium chloridedi-isobutylcresoxyethoxyethyldimethylbenzylammonium chloridep-di-isobutylphenoxyethoxyethyldimethylbenzylammonium chloridebenzoyltrimethylammonium bromide N-( butylcarbamoyl FUNGICIDALANTIBIOTICS VARIOUS N-( 3-nitrophenyl )-itaconimide phenoxy-acetic acidsodium p-dimethylamino-benzene diazosulphonate acrolein-phenylhydrazoneZ-chloracetaldehyde-(Z,4-dinitrophenyl)-hydrazone2-chlor-3-(tolylsulphonyl)propionitrile l-chlor-2-phenyl-pentan-diol(4,5 )-thione-( 3) p-nonylphenoxypolyethyIene-oxyethanol-iodine complex(a-nitromethyl)-o-chlorobenzylthioethylamine drochloride3-(p.-t.-butyl-phenylsulphonyl)-acrylonitrile octachlorocyclohexenonepentachlorobenzyl alcohol pentachlorobenzyl acetatepentachlorobenzaldehyde cyanhydrin 2-norcamphane-methanol2,6-bis-(dimethylaminomethyl)-cyclohexanone decachloroctahydro-l,3,4-metheno-2H- cyclobuta[cdl-pentalen-2-one l-( 3-chlorallyl )-3 ,5,7-triazal -azonia-adamantan chloride coal tar and blast furnace tarMIXTURES mixture nickelsulphate-maneb mixture maneb-mercaptobenzthiazolemixture zineb-mercaptobenzthiazole mixture zineb-nickelous chloridemixture zineb nickelous sulphate mixture ziram-basic copper sulphatemixture ziram-zinc-mercaptobenzthiazole mixture thiram-cadmium chloridehydrate mixture thiram-hydroxy-mercury chlorophenol mixturethiram-phenyl-mercuri acetate mixturepolyethylene-bis-thiuramsulphide-copper oxychloride mixturemethylarsine-bis-( dimethyldithiocarbamate )-ziram-thiram cadmiumdilactatethe reactions being carried out in either order of succession.

For example, thiophosgene may be reacted with the aniline and theresulting isothiocyanate, ARN=C=S, reacted with the amine of the formulaIII.

In the reverse order of succession a reactive derivative of thethiocarbonic acid may be reacted with an amine of the formula III, andthe resulting isothiocyanate of the formula reacted with the aforesaidaniline.

In a more simple and known manner the isothiocyanate of the formula IVmay be prepared by reacting 2,3-dichloropropylene-(1) with an inorganicthiocyanate, preferably an alkaline metal or ammonium thiocyanate. Ifdesired the chlorallyl group may be saturated with C1 or Br eitherbefore or after the formulation of the thiourea grouping.

The following examples illustrate the invention, the parts being byweight:

Example 1 Manufacture of:

C1 1111- C NH CII 185 parts of 4-chloro-3-trifluoromethyl-aniline in 200parts by volume of acetonitrile are added to 134 parts of[,B-chlorallyl] -isothiocyanate in 200 parts by volume of toluene and0.1 part of triethylene diamine. After heating the mixture for 20 hoursat C it is evaporated in vacuo to about 400 parts by volume, thendiluted with petroleum ether (boiling at 5070C filtered andrecrystallised from a mixture of toluene and petroleum ether (boiling at5070C). The product melts at 1 l5116C (compound No. 1).

In an analagous manner the following compounds of the formula V wereobtained:

'R NH 3 C Mi CH C CH Com R R R R; R Melting at pound No. C

2 H C1 C1 H H 81 83 3 H H H H H 93 95 4 H C H H H H 74 76 5 H CH H H H86 87 6 H CF H H H 79 81 7 H CF H CF H 124 127 8 CH Cl H H H 107 108 9C1 H NO H H 135 137 [0 Br H CH H Br 140 -141 11 H H C1 H H 97 98 12 H C1H H H 101 103 13 H C1 CH; H H 92 93 14 H N0 C1 H H 114- 117 15 C1 H C1C1 H 125 126 16 C1 H H C1 H 115 116 17 H H C H H H 1l3114 18 C1 C1 H H H121 122 19 Cl H C1 H H 131 132 20 H C1 H C1 H 124 125 Melting at 125126C (with decomposition) Gil-1r CH Br EXAMPLE 2 a. Dusting powder Equalparts of an active substance of the invention and precipitated silicawere finely ground. By admixture with kaolin or talc there can beproduced a dusting powder containing preferably 1-6% of activesubstance.

b. A sprinkling powder For preparing a sprinkling powder there are mixedtogether and finely ground, for example, the following components:

50 parts of the active substance of the invention parts of highlyadsorptive silica parts of Bolus alba (kaolin) 3 5 parts of sodiumbenzimidazole-6,3-disulphonate 3.5 parts of the reaction product ofp.tert.-

octylphenol and ethylene oxide.

l-benzyl-2-stearyl- 0. An emulsion concentrate EXAMPLE 3 In agreenhouse, Zucchetti plants were grown and sprayed onceprophylactically with an aqueous liquor containing 0.1% of the activesubstance. Two days later the plants so treated were infected withspores of Erysiphe cichoriac'earum DC. After 12 14 days the plantstreated with the test compound No. 1 showed an attack of 5% and theplants treated with compound No. 8 showed no attack, whereas theuntreated control plants suffered a 100% attack.

EXAMPLE 4 A mixture of equal parts of quartz sand and alumina wasinoculated with an aqueous suspension of conidia of Fusarium oxysporum,the mixture was charged into pots, and the pots were placed in a cabinetin a greenhouse. Two days later the pots were sown with melon seeds, andthen an aqueous liquor containing a quantity of active substance No. 2equivalent to a rate of kilogrammes per hectare was poured uniformlyover the pots.

The pots were kept suitably moist. After 14 days 87% of the sown plantsin the series of test treatments developed healthily, whereas 6%developed in the untreated control pots.

EXAMPLE 5 Compound No. Action 9 100% I4 100% I5 100% I6 100% l7 l0()% Inan analagous test with vine shoots as test plants and Borrvn's cinereaas test mould, compounds Nos. 21 and 22 each gave a 95% kill. Theiraction was systemic.

In an analagous test with celery (Apium graveolens) as test plant andSeptoria apii as test mould, compounds Nos. 3, 4 and 5 gave a kill of80% and respectively.

EXAMPLE 6 The active substances of the formula (1) exhibit a remarkablystrong action against gram-positive bacteria, especially againststaphylococci and streptococci.

The antibacterial activity was determined in dilution tests as follows:

BACTERIOSTASIS AND BACTERICIDIC 20 mg of active substance were dissolvedin 10 ml propylene glycol, of which 0.25 ml were added to 4.75 ml ofsterile glucose broth, and then diluted 1 10 in small tubes. Thesesolutions were then inoculated with a bacterium and incubated for 48hours at 37 C (bacteriostatics). After a test period of 24 hours 1 oese(drop) of these cultures was stroked on glucose-agar plates andincubated for 24 hours at 37 C (bactericides). After the stated periodsthe following limiting concentrations were measured in parts per millionof the bacteriostatics or bactericides:

Bacterium Compound No.2 No.7 No.6 No.9 No. 11 12 Trich.menta- 2.5 2.5 302O 20 20 grophytes E. coli 20 20 30 60 40 Asp.niger 60 Staphaureus 2.50.3 5.5 3 20 25 No.13 No.15 No.16 No.19 No.20 Trich.menta- I0 20 30 30 5grophytes E.coli 30 3O 20 Asp.niger 60 Staphaureus l0 2 20 30 0.6

means not tested.

EXAMPLE 7.

Determination of the minimum inhibiting concentration (MIC) againstbacteria and moulds in the gradient plate test.

The compounds of the formula 1. were mixed in the form of suitableformulations (for example, as solutions in dimethyl sulphoxide) ofdefinite concentration with warm brain heart infusion agar (bacteria) ormycophil agar (moulds). The liquid mixtures were poured onto asolidified wedge-shaped base layer of agar, and allowed to solidify.

By means of a Pasteur pipette the test organisms were applied in theform of lines perpendicularly to the gradient. After an incubationperiod of 24 hours at 37C. (bacteria), and 72 hours at 30C. (moulds),the lengths of the germinations grown on the lines of inoculation weremeasured and expressed in parts per million of active substance.

Com- Minimum inhibiting concentration in ppm. pound Nov BacteriostasisFungistasis Staphylococcus Asper- Tricho- Tricho- Epidermo- Micro aureusgillus phyton phyton phyton sporum niger mentagro rubrum floccosumgypseum -phytes l 0.4 60 0.8 5.5 20

I claim: 10 4. The method according to claim 2 in which R and 1. Amethod for controlling bacteria comprising ap plying to an area infestedwith said bacteria a detergent or cleaning composition comprisingbacteriostatically effective amount of a compound of the formula inwhich each of R R R R and R is hydrogen, chlorine, bromine, nitro, alkylof from 1 to 4 carbon atoms, or trifluoromethyl.

2. A method according to claim 1 in which the compound is in which twoof R R and R are chlorine or trifluoromethyl, and the other of R R and Ris hydrogen.

3. The method according to claim 2 in which R is trifluoromethyl, R ischlorine, and R is hydrogen.

R are chlorine, and R is hydrogen.

5. The method according to claim 1 in which, in the compound, R R R andR are hydrogen, and R is trifluoromethyl.

6. The method according to claim 2 in which R and R are trifluoromethyl,and R is hydrogen.

7. The method according to claim 1 in which, in the compound, R, ischlorine, R R and R are hydrogen, and R is nitro.

8. The method according to claim 1 in which, in the compound, R R R andR are hydrogen, and R is chlorine.

9. The method according to claim 1 in which, in the compound, R R R. andR are hydrogen, and R is chlorine.

10. The method according to claim 1 in which, in the compound, R R and Rare hydrogen, R is chlorine, and R is methyl.

11. The method according to claim 1 in which, in the compound, R R and Rare hydrogen, R is nitro, and R is chlorine.

12. The method according to claim 1 in which, in the compound, R R and Rare chlorine, and R and R are hydrogen.

13. The method according to claim 1 in which, in the compound, R and Rare chlorine, and R R and R are hydrogen.

14. The method according to claim 1 in which, in the compound, R and Rare chlorine, and R R and R are hydrogen.

15. The method according to claim 2 in which R and R are chlorine, and Ris hydrogen.

1. A METHOD FOR CONTROLLING BACTERIA COMPRISING APPLYING TO AN AREAINFESTED WITH SAID BACTERIA A DETERGENT OR CLEANING COMPOSIIONCOMPRISING BACTERIOSTATICALLY EFFECTIVE AMOUNT OF A COMPOUND OF THEFORMULA
 2. A method according to claim 1 in which the compound is
 3. Themethod according to claim 2 in which R2 is trifluoromethyl, R3 ischlorine, and R4 is hydrogen.
 4. The method according to claim 2 inwhich R2 and R3 are chlorine, and R4 is hydrogen.
 5. The methodaccording to claim 1 in which, in the compound, R1, R3, R4 and R5 arehydrogen, and R2 is trifluoromethyl.
 6. The method according to claim 2in which R2 and R4 are trifluoromethyl, and R3 is hydrogen.
 7. Themethod according to claim 1 in which, in the compound, R1 is chlorine,R2, R4 and R5 are hydrogen, and R3 is nitro.
 8. The method according toclaim 1 in which, in the compound, R1, R2, R4 and R5 are hydrogen, andR3 is chlorine.
 9. The method according to claim 1 in which, in thecompound, R1, R3, R4 and R5 are hydrogen, and R2 is chlorine.
 10. Themethod according to claim 1 in which, in the compound, R1, R4 and R5 arehydrogen, R2 is chlorine, and R3 is methyl.
 11. The method according toclaim 1 in which, in the compound, R1, R4 and R5 are hydrogen, R2 isnitro, and R3 is chlorine.
 12. The method according to claim 1 in which,in the compound, R1, R3 and R4 are chlorine, and R2 and R5 are hydrogen.13. The method according to claim 1 in which, in the compound, R1 and R4are chlorine, and R2, R3 and R5 are hydrogen.
 14. The method accordingto claim 1 in which, in the compound, R1 and R3 are chlorine, and R2, R4and R5 are hydrogen.
 15. The method according to claim 2 in which R2 andR4 are chlorine, and R3 is hydrogen.